JP4167254B2 - Intermediates for the synthesis of metallocenes containing aryl-substituted indenyl derivatives as ligands and methods of use thereof - Google Patents

Abstract

Catalysts consisting of a metallocene of formula (I) and a cocatalyst are claimed, M<1> = a Group IVb, Vb or VIb metal; R<1>, R<2> = H, 1-10C alkyl or alkoxy, 6-10C aryl or aryloxy, 2-10C alkenyl, 7-40C aralkyl or alkaryl, 8-40C aralkenyl, OH or halogen; R<3> = H, halogen, optionally halogenated 1-10C alkyl, 6-10C aryl, N(R<16>)2, SR<16>, OSi(R<16>)3, Si(R<16>)3 or P(R<16>)2 (with R<16> = halogen, 1-10C alkyl or 6-10C aryl); R<4>-R<12> = as for R<3>, or adjacent groups may form part of one or more aromatic or aliphatic rings, or the groups R<5> and R<8> or R<12> may form such rings with the attached atoms; R<13> = -X-, -X-X-, -Y-Y-, -O-X-O- -Y-, -O-X-, -Y-X-, -Y-Y-Y-, =BR<14>, =AlR<14>, -O-, -S-, =SO, =SO2, =NR<14>, =CO, =PR<14> or =P(O)R<14>; X = -M<2>R<14>R<15>-; Y = -CR<14>R<15>; R<14>, R<15> = H, halogen, 1-10C alkyl, fluoroalkyl or alkoxy, 6-10C aryl, fluoroaryl or aryloxy, 2-10C alkenyl, 7-40C aralkyl or alkaryl, or 8-40C aralkenyl, or R<14> + R<15> + the attached atoms may form ring(s); M<2> = silicon, germanium or tin. Also claimed are: (i) polyolefins obtained by (co)polymerisation of olefins of formula Ra-CH=CH-Rb (with Ra, Rb = H or 1-14C hydrocarbyl, or Ra + Rb may form part of one or more rings) at -60 to 200 degrees C and 0.5-100 bar in solution, suspension or gas phase, in presence of these catalysts; (ii) a process for the production of metallocenes (I); and (iii) intermediate indanones, indenes and bridged ligand systems formed in this process.

Description

Detailed Description of the Invention

Industrial application fields

  The present invention relates to a novel metallocene containing an aryl-substituted indenyl derivative as a ligand. The metallocene can be used very advantageously as a catalyst component in the production of polyolefins having high isotacticity, narrow molecular weight distribution and very high molecular weight.

Problems to be solved by the prior art and the invention

High molecular weight polyolefins are particularly important for the production of films, sheets, or large hollow articles or molded articles (eg pipes).
According to the literature, soluble metallocene compounds are used in combination with aluminoxanes or other cocatalysts, whose Lewis acidity can convert neutral metallocenes to cations and stabilize them. Manufacturing polyolefins.

  When a soluble metallocene compound based on bis (cyclopentadienyl) dialkylzirconium or bis (cyclopentadienyl) zirconium dihalide is combined with an aluminoxane oligomer, ethylene has good activity and propylene has moderate activity. It can be polymerized. A polyethylene having a narrow molecular weight distribution and a medium molecular weight is obtained. Polypropylene produced in this way is atactic and has a rather low molecular weight.

  The production of isotactic polypropylene is achieved by the combined use of ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride and aluminoxane in suspension polymerization (see EP 185 918). ). The polymer thus obtained has a narrow molecular weight distribution. The disadvantage of the process is that only polymers with very low molecular weight are produced at industrially applied polymerization temperatures.

  Special preactivation methods have also been proposed that combine metallocenes and aluminoxanes, which greatly increase the activity of the catalyst system and significantly improve the polymer's grain morphology ( DE 37 26 067). However, the molecular weight is hardly increased by this preactivation method.

Catalysts based on ethylenebisbisindenylhafnium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) hafnium dichloride, and methylaluminoxane are also known, and by using this catalyst A relatively high molecular weight polypropylene can be produced by suspension polymerization [J. Am. Chem. Soc. (1987), 109 , 6544]. However, the grain morphology of the polymer obtained in this way under industrially applied polymerization conditions is not satisfactory and the activity of the catalyst system used is also relatively low. Due to the high cost of the catalyst, polymerization using these catalyst systems is expensive.

  Aromatic π-ligands anchored by bridges have substituents in the 2-position (see DE 40 35 886) or in the 2- and 4-positions (see DE 41 28 238) By using metallocene, a significant increase in molecular weight was achieved.

  By using aromatic π-ligands having substituents in the 2-, 4-, and 6-positions (see DE 41 39 596) and also aromatic π-ligands of the 4,5-benzoindenyl type Further increases in molecular weight were achieved by using (see DE 41 39 595).

  The metallocenes with substituents are already quite effective at a polymerization temperature of 70 ° C. However, the molecular weight obtained at an industrially optimal polymerization temperature of 70 ° C. is still too low for many industrial applications (eg for pipes and large hollow articles, and in particular for the production of textile polymers). .

  Polymerization must be carried out at the highest possible reaction temperature under the constraints of cost-effective large-scale production. This is because the heat of reaction generated at a relatively high polymerization temperature can be dissipated using very little cooling medium. Therefore, the cooling water circuit can be made on a considerably small scale.

  A disadvantage that arises when using a soluble (homogeneous) metallocene / methylaluminoxane catalyst system in a process where the polymer is formed as a solid is that thick deposits form on the reactor walls and stirrer. It is. These deposits are formed by agglomeration of polymer particles when the metallocene, aluminoxane, or both are in the form of a solution in a suspending medium. These types of deposits in the reactor system must be removed periodically. This is because the deposit immediately becomes a considerable thickness, has a high strength, and prevents heat exchange with the cooling medium.

  It is therefore advantageous to use the metallocene in a supported form. An efficient and simple method for supporting metallocenes has been proposed that can be widely used in any polymerization process (see EP 92 107331.8).

  A further disadvantage of stereospecific polymerization of prochiral monomers (eg propylene) using metallocene catalysts is that the isotacticity is relatively low, which results in the case of isotactic polypropylene. The melting point is lowered. When a specific metallocene having substituents at the 2-position and 4-position, particularly rac-dimethylsilylbis (2-methyl-4-isopropylindenyl) zirconium dichloride and methylaluminoxane, is combined with propylene, A polymer with tacticity (and thus a high melting point) is obtained (see DE 41 28 238). Nevertheless, the melting point achieved is too low for the polymerization temperature (eg 70 ° C.) applied industrially for some industrial applications.

However, there are industrial applications where a low melting point is required.
The object of the present invention is to find a process and / or catalyst system for producing polymers with very high molecular weight [in the case of isospecific polymerization of prochiral monomers, polymers with high isotacticity are used. To obtain in high yield]. The use of a carrier prevents the known drawbacks from the prior art caused by the formation of deposits and a high proportion of fine particles. When hydrogen is used as a molecular weight regulator, it is possible to cover the entire range of industrially interesting molecular weights with a single metallocene.

  Metallocenes containing specific indenyl derivatives as ligands are suitable catalysts for the production of high molecular weight polyolefins (especially isotactic polyolefins with very high molecular weight and very high isotacticity by using prochiral monomers). Component).

  Reaction of these soluble metallocenes with the supported organoaluminum catalyst component provides a catalyst system that does not require additional promoters for activation and completely prevents the formation of reactor deposits. .

  Accordingly, the present invention provides a compound of formula I

(Where
M ¹ is a metal from groups IVb, Vb, or VIb of the periodic table;
R ¹ and R ² are the same or different and are a hydrogen atom, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₁₀ aryl group, a C ₆ -C ₁₀ aryloxy group, a C ₂ -C ₁₀ alkenyl group, C ₇ -C ₄₀ arylalkyl group, C ₇ -C ₄₀ alkylaryl group, C ₈ -C ₄₀ arylalkenyl group, an OH group or a halogen atom;
The two R ³ groups are the same or different and are a hydrogen atom, a halogen atom, an optionally halogenated C ₁ -C ₁₀ alkyl group, a C ₆ -C ₁₀ aryl group, a —NR ¹⁶ ₂ group, a —SR ¹⁶ Group, —OSiR ¹⁶ ₃ group, —SiR ¹⁶ ₃ group, or —PR ¹⁶ ₂ group, wherein R ¹⁶ is a halogen atom, a C ₁ -C ₁₀ alkyl group, or a C ₆ -C ₁₀ aryl group. Is;
R ^{4 to} R ¹² are the same or different and are as defined for R ³ , or adjacent groups of R ^{4 to} R ¹² together with the atoms connecting them, one or more aromatic rings Or an aliphatic ring, or R ⁵ and R ⁸ or R ⁵ and R ¹² together with the atoms connecting them form one aromatic or aliphatic ring; and R ¹³ is ,

= BR ¹⁴ , = AIR ¹⁴ , -Ge-, -O-, -S-, = SO, = SO ₂ , = NR ¹⁴ , = CO, = PR ¹⁴ , or = P (O) R ¹⁴ , At this time, R ¹⁴ and R ¹⁵ are the same or different, and are a hydrogen atom, a halogen atom, a C _{1 to} C ₁₀ alkyl group, a C _{1 to} C ₁₀ fluoroalkyl group, a C _{1 to} C ₁₀ alkoxy group, or a C _{6 to} C _10. aryl group, C ₆ -C ₁₀ fluoroaryl group, C ₆ -C ₁₀ aryloxy group, C ₂ -C ₁₀ alkenyl group, C ₇ -C ₄₀ arylalkyl group, C ₇ -C ₄₀ alkylaryl group, or C _8, -C ₄₀ or an aryl alkenyl group, or R ¹⁴ and R ¹⁵ are, in each case, together with the atoms connecting them form one or more rings, and M ² is silicon, germanium, Or tin)
It is related with the compound shown by these.

The present invention further relates to the formula R ^a —CH═CH—R ^b , wherein R ^a and R ^b are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms, Alternatively, R ^a and R ^b together with the atoms connecting them can form one or more rings) at a temperature of −60 to 200 ° C. and 0.5 to 100 bar. Of an olefin polymer by polymerization or copolymerization in the presence of a catalyst formed from a metallocene as a transition metal compound and a co-catalyst in a solution, suspension, or gas phase at a pressure of Wherein the metallocene is the compound of formula I.

  The compounds according to the invention have the formula I

Where M ¹ is a metal from groups IVb, Vb, or VIb of the periodic table, such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten. Preferred is zirconium, hafnium, or titanium.

R ¹ and R ² are the same or different and are a hydrogen atom, a C ₁ -C ₁₀ alkyl group (preferably a C ₁ -C ₃ alkyl group), a C ₁ -C ₁₀ alkoxy group (preferably a C ₁ -C ₃ alkoxy group). Group), C ₆ -C ₁₀ aryl group (preferably C ₆ -C ₈ aryl group), C ₆ -C ₁₀ aryloxy group (preferably C ₆ -C ₈ aryloxy group), C ₂ -C ₁₀ alkenyl group (Preferably C ₂ -C ₄ alkenyl group), C ₇ -C ₄₀ arylalkyl group (preferably C ₇ -C ₁₀ arylalkyl group), C ₇ -C ₄₀ alkylaryl group (preferably C ₇ -C ₁₂ alkyl) aryl group), C ₈ -C ₄₀ arylalkenyl group (preferably a C ₈ -C ₁₂ arylalkenyl group), or a halogen atom (preferably a chlorine atom).

R ^{3 to} R ¹² are the same or different and are a hydrogen atom, a halogen atom (preferably a fluorine, chlorine, or bromine atom), and a C _{1 to} C ₁₀ alkyl group (preferably C _{1 to} C) that may be halogenated. ₄ alkyl group), C ₆ -C ₁₀ aryl group (preferably C ₆ -C ₈ aryl group), —NR ¹⁶ ₂ group, —SR ¹⁶ group, —OSiR ¹⁶ ₃ group, —SiR ¹⁶ ₃ group, or —PR ¹⁶ a ₂ group, wherein R ¹⁶ in this case, a halogen atom (preferably chlorine atom), C ₁ -C ₁₀ alkyl group (preferably C ₁ -C ₄ alkyl group), or a C ₆ -C ₁₀ aryl group (preferably, C ₆ -C ₈ aryl group) a.

The adjacent groups of R ^{4 to} R ¹² , together with the atoms connecting them, are aromatic rings (preferably 6-membered aromatic rings) or aliphatic rings (preferably 4- to 8-membered aliphatic rings). Can be formed.

R ¹³ is

^{= BR 14, = AIR 14,} -Ge -, - O -, - S -, = SO, = SO 2, = NR 14, = CO, a = PR ¹⁴ or ^{= P (O) R 14,} , preferably Is

= BR ¹⁴ , = AIR ¹⁴ , -Ge-, -O-, -S-, = SO, = SO ₂ , = NR ¹⁴ , = CO, = PR ¹⁴ , or = P (O) R ^14. When R ¹⁴ and R ¹⁵ are the same or different, a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ alkyl group (preferably a C ₁ -C ₄ alkyl group, particularly a methyl group), a C ₁ -C ₁₀ fluoroalkyl group (Preferably CF ₃ group), C ₆ -C ₁₀ aryl group (preferably C ₆ -C ₈ aryl group), C ₆ -C ₁₀ fluoroaryl group (preferably pentafluorophenyl group), C ₁ -C ₁₀ alkoxy groups (preferably C ₁ -C ₄ alkoxy groups, especially methoxy), C ₂ -C ₁₀ alkenyl group (preferably C ₂ -C ₄ alkenyl group), C ₇ -C ₄₀ arylalkyl group (preferably C ₇ ~ C ₁₀ arylalkyl group), C ₈ ~C ₄₀ Ariruaru Or alkenyl group (preferably C ₈ -C ₁₂ arylalkenyl group) (preferably C ₇ -C ₁₂ alkylaryl group), or a C ₇ -C ₄₀ alkylaryl group is, or R ¹⁴ and R ¹⁵ are each In some cases, the atoms connecting them form one or more rings.

M ² is silicon, germanium or tin, preferably silicon or germanium.
For compounds of formula I,
M ¹ is zirconium or hafnium;
R ¹ and R ² are the same and are a C ₁ -C ₃ alkyl group or a halogen atom;
The two R ³ groups are identical and are C ₁ -C ₄ alkyl groups;
R ^{4 to} R ¹² are the same or different and are hydrogen or a C _{1 to} C ₄ alkyl group; and R ¹³ is

Wherein M ² is silicon or germanium and R ¹⁴ and R ¹⁵ are the same or different and are C ₁ -C ₄ alkyl groups or C ₆ -C ₁₀ aryl groups;
Is preferred.

For compounds of formula I it is further preferred that R ⁴ and R ⁷ are hydrogen and R ⁵ , R ⁶ and R ^{8 to} R ¹² are C _{1 to} C ₄ alkyl groups or hydrogen.
For compounds of Formula I, a M ¹ is zirconium, an R ¹ and R ² are identical a chlorine atom, a C ₁ -C ₄ alkyl radical R ³ are the same, R ⁴ And R ⁷ are hydrogen, R ⁵ , R ⁶ , and R ^{8 to} R ¹² are the same or different, are C _{1 to} C ₄ alkyl groups or hydrogen, and R ¹³ is

It is particularly preferred that M ² is silicon and R ¹⁴ and R ¹⁵ are the same or different and are a C ₁ -C ₄ alkyl group or a C ₆ -C ₁₀ aryl group.
The production of metallocene I is carried out by processes known in the literature and is shown in the following reaction scheme.

Halogenated derivatives of 2-phenylbenzyl of formula A are commercially available or can be prepared by methods known in the literature.
Conversion to the compound of formula B is performed by reacting with a substituted malonic ester under basic conditions (eg, in an ethanol solution of sodium ethoxide).

  The compound of formula B is hydrolyzed with an alkali metal hydroxide (eg, potassium hydroxide or sodium hydroxide), and the resulting dicarboxylic acid is decarboxylated by treatment at elevated temperature to give the compound of formula C.

Corresponding ring closure for obtaining phenyl-1-indanone which is chlorinated reagent (e.g., SOCl ₂₎ to produce the corresponding acid chloride is reacted with, subsequently Friedel-Crafts catalyst in an inert solvent of the formula D By cyclization using (eg AlCl ₃ or polyphosphoric acid in methylene chloride or CS ₂ ).

  Conversion to the 7-phenylindene derivative of formula E can be accomplished by using a hydride ion transfer agent (eg, sodium borohydride or lithium aluminum hydride) or hydrogen and an appropriate solvent in an inert solvent (eg, diethyl ether or tetrahydrofuran). Reduction using a suitable catalyst to produce the corresponding alcohol, followed by a dehydration reaction under acidic conditions (eg, in the presence of p-toluenesulfonic acid or aqueous mineral acid) or for dehydration This is done by reacting with a substance (eg, magnesium sulfate, anhydrous copper sulfate, or molecular sieve).

  The preparation of the ligand system of formula G, the conversion to the bridged chiral metallocene of formula H, and the isolation of the desired racemate is as already known. A phenylindene derivative of formula E is deprotonated using a strong base (eg, butyllithium or potassium hydride) in an inert solvent and reacts with a reagent of formula F to produce a ligand system of formula G. . The ligand system is subsequently deprotonated with 2 equivalents of a strong base (eg, butyllithium or potassium hydride) in an inert solvent and the appropriate metal tetrachloride (eg, zirconium tetrachloride) in a suitable solvent. ). Suitable solvents include aliphatic or aromatic solvents (eg, hexane or toluene), ether solvents (eg, tetrahydrofuran or diethyl ether), halogenated hydrocarbons (eg, methylene chloride), and halogenated aromatic hydrocarbons (eg, o-dichlorobenzene). The racemate and meso form are separated by extraction or recrystallization using an appropriate solvent.

The derivation to obtain the metallocene of formula I can be effected, for example, by reacting with an alkylating agent (eg methyllithium).
The metallocene I according to the present invention is a highly active catalyst component for the polymerization of olefins. Preference is given to using chiral metallocenes as racemates. However, the (+) or (−) pure enantiomers can also be used. The use of pure enantiomers allows the production of optically active polymers. However, the meso form of metallocene must be removed. This is because the polymerization active center (metal atom) in these compounds is no longer chiral due to mirror symmetry at the central metal atom, and therefore high isotactic polymers can no longer be obtained. When the meso form is not removed, an atactic polymer is formed in addition to the isotactic polymer. For certain applications (eg soft molding) it may be desirable not to remove the meso form.

  According to the invention, the cocatalyst used is of the formula IIa as a linear type

Of formula IIb as aluminoxane and / or cyclic type

The aluminoxane is preferred. At this time, in the formulas IIa and IIb, the plurality of R ¹⁷ groups are the same or different and are C ₁ -C ₆ alkyl groups, C ₆ -C ₁₈ aryl groups, benzyl groups, or hydrogen atoms, and p is 2-50. (Preferably an integer of 10 to 35).

The radicals R ¹⁷ are preferably identical and are preferably methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
When the groups R ¹⁷ are different, R ¹⁷ is preferably methyl and hydrogen, or methyl and isobutyl. At this time, hydrogen and isobutyl are preferably present in an amount of about 0.01 to 40% (the number of groups R ¹⁷ ).

The aluminoxane can be produced by various methods according to a known process. For example, one method is to combine an aluminum hydrocarbon compound and / or hydrido aluminum hydrocarbon compound and water in an inert solvent (eg, toluene) [gas, solid, liquid, or combined form (eg, crystalline). (As water)]. To make an aluminoxane containing different groups R ¹⁷ , two different trialkylaluminum compounds are reacted with water, for example according to the desired composition.

The exact structure of aluminoxanes IIa and IIb is not clear.
Regardless of the method of preparation, all aluminoxane solutions commonly contain various contents of unreacted aluminum starting compound in free form or as an adduct.

  Prior to use of the metallocene in the polymerization reaction, the metallocene can be reactivated by an aluminoxane of formula IIa and / or IIb. This greatly increases the polymerization activity and improves the grain morphology. The reactivation of the transition metal compound is performed in solution. The metallocene is preferably dissolved in an inert hydrocarbon solution of aluminoxane. Suitable inert hydrocarbons are aliphatic hydrocarbons or aromatic hydrocarbons. Toluene is preferred.

The concentration of the aluminoxane in the solution is about 1% by weight to the saturation limit, preferably 5 to 30% by weight, in each case based on the total weight of the solution. The metallocene can be used in the same concentration but is preferably used in an amount of aluminoxane per mol 10 ^-4 to 1 mol. The preactivation is performed for 5 minutes to 60 hours (preferably 5 to 60 minutes). The temperature is -78 to 100 ° C (preferably 0 to 70 ° C).

  Prepolymerization can be carried out using metallocene and preferably using the olefin (or one of several olefins) used in the polymerization.

  Metallocenes can also be applied to the support. Suitable carrier materials include, for example, silica gel, aluminum oxide, solid aluminoxane, or other inorganic carrier materials (eg, magnesium chloride). Other suitable carrier materials include polyolefin powder in fine powder form.

  Preferably, a support (eg, silica gel, aluminum oxide, solid aluminoxane, other inorganic support material, or polyolefin powder in fine powder form) is co-catalyzed (ie, an organoaluminum compound) and then reacted with the metallocene.

  Inorganic supports that can be used are oxides produced by flame pyrolysis by the combustion of halogen elements in an oxygen-hydrogen flame, or have a specific particle size distribution and a specific particle shape. It can also be produced as a solid silica gel.

  The supported cocatalyst can be produced, for example, by the following method according to the description in EP 92 107 331.8. An explosion-proof stainless steel reactor equipped with a 60 bar pump system is used to supply inert gas and to control the temperature by means of a separate cooling circuit via jacket cooling and heat exchange with a forced circulation system. A pump system draws the reactor contents through a connection at the bottom of the reactor, forces it into the mixer, and passes back through the heat exchanger to the reactor through the ascending line. Mixing is designed such that the supply line includes a narrow tube crossing, at which time an increased flow rate is generated, and in the turbulence zone, a narrow supply line is provided axially and opposite to the flow direction; In either case, it can be supplied in the form of a cycle with a specified amount of water under a pressure of 40 bar of argon. The reaction is monitored by a sampler in the pump circuit.

In general, however, other reactors are also suitable.
In the reactor having a volume of 16 dm ^3, it introduces a decane 5 dm ³ under inert conditions. 0.5 dm ³ (= 5.2 mol) of trimethylaluminum is added at 25 ° C. 250 g of silica gel SD3216-30 (Grace AG) previously dried at 120 ° C. in an argon fluidized bed is weighed into the reactor via a solid funnel and distributed homogeneously by means of a stirrer and pump system. . A total of 76.5 g of water is introduced into the reactor at 0.1 cm ³ every 15 seconds for 3.25 hours. The pressure caused by argon and the evolved gas is kept constant at 10 bar by means of a pressure regulating valve. After all the water has been introduced, the pump system is switched off and stirring is continued for an additional 5 hours at 25 ° C.

The supported promoter thus obtained is used as a 10% strength suspension in n-decane. The aluminum content is 1.06 mmol Al per cm ³ of the suspension. The isolated solid contains 31% aluminum and the suspending medium contains 0.1% aluminum.

Another method for making supported promoters is described in EP 92 107331.8.
The metallocene according to the invention is then applied to the supported promoter by stirring the dissolved metallocene together with the supported promoter. The solvent is removed and replaced with a hydrocarbon in which both the cocatalyst and the metallocene are insoluble.

  The reaction for obtaining the supported catalyst system is carried out at a temperature of -20 to + 120 ° C (preferably 0 to 100 ° C, particularly preferably 15 to 40 ° C). The cocatalyst as a suspension of 1 to 40 wt% concentration (preferably 5 to 20 wt% concentration) in an aliphatic inert suspending medium (e.g. n-decane, hexane, heptane or diesel oil). The metallocene is reacted with the supported promoter by mixing a metallocene solution in an inert solvent (eg, toluene, hexane, heptane, or dichloromethane) or a finely divided solid metallocene. Conversely, a metallocene solution can be reacted with a solid promoter.

The reaction is carried out by powerful mixing under inert conditions, for example at an Al / M ¹ molar ratio of 100/1 to 10,000 / 1 (preferably 100/1 to 3000/1) for 5 to 120 minutes. It is carried out by stirring with a reaction time of preferably 10 to 60 minutes, particularly preferably 10 to 30 minutes.

  During the reaction time to make the supported catalyst system, particularly in the use of the metallocenes of the present invention having maximum absorption in the visible region, a color change of the reaction mixture occurs, which is used to monitor the progress of the reaction. be able to.

  When the reaction time is complete, the supernatant solution is separated, for example, by filtration or decantation. In order to remove soluble components in the catalyst formed, and in particular to remove unreacted metallocene (and therefore soluble metallocene), the remaining solids are treated with an inert suspension medium (e.g. toluene, n-decane, hexane, diesel oil, or dichloromethane).

  The supported catalyst system thus prepared can be dried as a powder under reduced pressure or resuspended using a solvent and polymerized as a suspension in one of the above inert suspension media. It can also be measured in the system.

According to the present invention, instead of the aluminoxane, or in addition to an aluminoxane, wherein ^{_{R 18 x NH 4-x BR}} 19 4, R 18 x PH 4-x BR 19 4, R 18 3 CBR 19 4, and BR ¹⁹ _The compound represented by ₃ can be used as a suitable promoter. In these formulas, x is a number from 1 to 4 (preferably 3) and the radicals R ¹⁸ are the same or different (preferably the same) and are C ₁ -C ₁₀ alkyl, C ₆ -C ₁₈ aryl. Or two R ¹⁸ groups together with the atoms connecting them form a ring, the groups R ¹⁹ being the same or different (preferably the same) and substituted with alkyl, haloalkyl or fluorine atoms C ₆ -C ₁₈ aryl optionally. Particularly preferably R ¹⁸ is ethyl, propyl, butyl or phenyl and R ¹⁹ is phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (EP 277 003 EP 277 004 and EP 426 638).

  When the above promoter is used, the actual (active) polymerization catalyst comprises the reaction product of one of the compounds and a metallocene. For this reason, the reaction product is preferably prepared outside the polymerization reactor in a separate step using a suitable solvent in advance.

  In general, the co-catalyst according to the invention can be any compound capable of converting neutral metallocenes into cations and stabilizing the cations (“Substituted Active Coordination”) due to its Lewis acidity. ). Furthermore, the cocatalyst or the anion formed therefrom must not undergo further reaction with the metallocene cation formed (see EP 427 697).

  In order to remove catalyst poisons present in the olefin, it is desirable to purify using an alkylaluminum compound (for example, trimethylaluminum or triethylaluminum). This purification operation can be carried out in the polymerization system itself, or it can be introduced into the polymerization system after contacting the olefin with the Al compound and then removed again.

The polymerization or copolymerization is carried out in solution, in suspension, or in the gas phase in one or more steps in a continuous or batch manner, -60 to 200 ° C (preferably 30 to 80 ° C, particularly preferably At a temperature of 50-80 ° C.) according to known methods. Polymerization or copolymerization is carried out using an olefin of the formula R ^a —CH═CH—R ^b . In the above formula, R ^a and R ^b are the same or different and are a hydrogen atom or an alkyl group having 1 to 14 carbon atoms. However, R ^a and R ^b , together with the carbon atoms connecting them, can alternately form a ring. Examples of such olefins include ethylene, propylene, 1-butene, 1-hexane, 4-methyl-1-pentene, 1-octene, norbornene, and norbornadiene. In particular, propylene and ethylene are polymerized.

  If necessary, hydrogen is added as a molecular weight regulator and / or to increase activity. The overall pressure of the polymerization system is 0.5 to 100 bar. The polymerization is preferably carried out in the pressure range of industrial interest of 5 to 64 bar.

The metallocene is used in the polymerization at a concentration of 10 ⁻¹³ to 10 ⁻⁸ mol (preferably 10 ⁻⁴ to 10 ⁻⁷ mol) of transition metal per 1 dm ^{3 of} solvent or 1 dm ^{3 of} reactor volume. The aluminoxane is used at a concentration of 10 ⁻⁵ to 10 ⁻¹ mol (preferably 10 ⁻⁴ to 10 ⁻² mol) per ¹ dm ^{3 of} solvent or ¹ dm ^{3 of} reactor volume. The other promoters described above are used in approximately equimolar amounts with respect to the metallocene. In general, however, higher concentrations are possible.

  When the polymerization is carried out as suspension polymerization or solution polymerization, an inert solvent commonly used for Ziegler low pressure processes is used. For example, the polymerization is performed in an aliphatic or alicyclic hydrocarbon (eg, propane, butane, hexane, heptane, isooctane, cyclohexane, and methylcyclohexane). In addition, benzine and hydrogenated diesel oil fractions can be used. Toluene can also be used. The polymerization is preferably performed using a liquid monomer.

If an inert solvent is used, the monomer is metered in gaseous or liquid form.
The polymerization can be applied for any desired reaction time. This is because the catalyst system used according to the present invention shows little decrease in time dependence with respect to the polymerization activity.

Before adding the catalyst, the polymerization system should be disabled, especially before adding the supported catalyst system (including the metallocene according to the invention, the supported co-catalyst or metallocene according to the invention and the organoaluminum compound in a form supported on polyolefin fines). Still other alkylaluminum compounds (eg, trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, or isochoric) for activation (eg, to remove catalyst poisons present in the olefin) Prenylaluminum) may be introduced into the reactor. The compound is added to the polymerization system at a concentration of 100 to 0.01 mmol of Al per kg of reactor contents. Triisobutylaluminum and triethylaluminum are preferably added at a concentration of 10 to 0.1 mmol of Al per kg of reactor contents. This makes it possible to select the Al / M ¹ molar ratio at a low level in the synthesis of the supported catalyst system.

  In general, however, it is not necessary to use further substances to promote the catalysis of the polymerization reaction. That is, the catalyst system of the present invention can be used as a single catalyst for the polymerization of olefins.

  The process according to the invention is characterized in that very high molecular weight polymers can be obtained by using the aforementioned metallocenes, and in the case of prochiral monomers, extremely high molecular weights and very high stereotacticity. A polymer having a high catalytic activity in a temperature range (50 to 80 ° C.) of particular industrial interest.

  In particular, the zirconocene according to the present invention is characterized in that in the case of stereospecific polymerization of prochiral olefins (eg polypropylene), a polymer with high isotacticity is obtained.

  In particular, in the case of isospecific polymerization of propylene, isotactic polypropylene having a long isotactic sequence length and a high melting point is obtained.

Furthermore, the supported catalyst system of the present invention prevents deposits from adhering to the reactor walls.
Hereinafter, the present invention will be described in more detail with reference to examples.
The all glass device was dried under reduced pressure and flushed with argon. All manipulations were performed in a Schlenk vessel from which moisture and oxygen had been removed. In each case, the solvent used was freshly distilled over an Na / K alloy in an argon atmosphere and stored in a Schlenk container.

The determination of the Al / CH ₃ ratio in aluminoxane is determined by decomposition of the sample using H ₂ SO ₄ and measurement of the volume of hydrolyzed gas produced, and by complexometric titration of aluminum in the sample, and dissolved to Schwarzen. The Bach method (Schwarzenbach method) was used.

For Examples 3-5 using a supported aluminum compound (methylaluminoxane on silica gel), hereinafter referred to as “MAO on SiO ₂ ”, a suspension of about 10 wt% concentration in n-decane. Was made. This suspension contained 60 mg Al per cm ³ according to aluminum measurements.

For Examples 26-30 using a supported aluminum compound (methylaluminoxane on silica gel, SD3216-30 / Grace)-hereinafter referred to as “FMAO on SiO ₂ ” —20 wt% in solids A solventless powder containing aluminum was used.

For the examples of suspension polymerization and bulk polymerization using unsupported metallocene, toluene-soluble methylaluminoxane was used as a 10 wt% toluene solution. This solution contained 36 mg Al per cm ³ according to aluminum measurements. The average degree of oligomerization was n = 20 according to the freezing point depression in benzene. For the methylaluminoxane toluene soluble, Al: CH ₃ ratio of 1: was measured to be 1.55.

Use the following ellipsis:
Viscosity index displayed at VI = cm ³ / g
M _w = weight average molecular weight expressed in g / mol (measured by gel permeation chromatography)
M _w / M _n = molecular weight dispersion P. = Melting point expressed in ° C (measured by DSC, heating / cooling rate 20 ° C / min)
II = isotactic index (II = mm + 1.2 mr, measured by ¹³ C-NMR spectroscopy)
MFI 230/5 = melt flow index expressed in dg / min (measured according to DIN 53735)
BD = polymer bulk density expressed in g / dm ³

Synthesis of metallocene I used in the polymerization examples (starting materials used are commercially available):
A. Rac-dimethylsilylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride (5)
1. (±) -2- (2-Phenylbenzyl) propionic acid (1)
To a mixture of 6.5 g (0.285 mol) of sodium in 160 cm ³ of H ₂ O free EtOH, 48.6 g (0.279 mol) of diethyl methyl malonate was added dropwise. Then, 70.4 g (0.285 mol) of 2-phenylbenzyl bromide mixed in 20 cm ³ of H ₂ O-free EtOH was added dropwise and the batch was refluxed for 3 hours. The solvent was stripped and 200 cm ³ of H ₂ O was added to the residue. The organic phase was separated and the aqueous phase was saturated with NaCl and extracted twice with 200 cm ³ of Et ₂ O each time. The combined organic phase of the extracts was dried over MgSO ₄ .

The residue after stripping the solvent was mixed with 500 cm ³ of EtOH and 50 cm ³ of H ₂ O, and 56 g (1 mol) of KOH was added. The reaction mixture was refluxed for 4 hours. The solvent was stripped, 500 cm ³ of H ₂ O was added to the residue, and the solution was acidified to pH 1 with concentrated hydrochloric acid. The resulting precipitate was filtered with suction and heated in a bulb tube at 250 ° C. with vigorous bubbling for 30 minutes to give 58.5 g (85%) of 1 as a viscous oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 11.7 (s, 1 H, COOH) 7.1 to 7.5 (m, 9 H, arom. H), 2.3 to 3.2 (m, 3 H, CH and CH ₂ ), 0.9 (d, 3H, CH ₃ )
2. (±) -2-Methyl-4-phenylinden-1-one (2)
A solution obtained by dissolving 58 g (0.242 mol) of 1 in 60 cm ³ (0.83 mol) of thionyl chloride was stirred at room temperature for 18 hours. Excess thionyl chloride is removed at 10 mbar and, in each case, by repeated dissolution in 100 cm ³ of toluene, the sticky residue of thionyl chloride is removed from the oily residue and stripped at reduced pressure. It was.

150 cm ³ of toluene was mixed with the obtained acid chloride, and this was added dropwise at 10 ° C. to a suspension of 48 g (0.363 mol) of AlCl ₃ suspended in 400 cm ³ of toluene. After the addition was complete, the mixture was refluxed for an additional 3 hours. The reaction mixture was poured into 500 g of ice and acidified with concentrated hydrochloric acid to pH 1. The organic phase was separated and the aqueous phase was extracted three times with 100 cm ³ of Et ₂ O each time. The organic phases were combined, washed with saturated aqueous NaHCO ₃ and NaCl, and dried over MgSO ₄ to give 50.4 g (93%) of 2 which was used in the next reaction without further purification. did.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.2 to 7.8 (m, 8H, arom.H), 3.3 (dd, 1H, β-H), 2.5 to 2.9 ( m, 2 H, α- and β-H), 1.3 (d, 3H, CH ₃ )
3. 2-Methyl-7-phenylindene (3)
50 g (0.226 mmol) of 2 is dissolved in 450 cm ³ of THF / MeOH (2: 1) and 12.8 g (0.34 mol) of sodium borohydride are added in portions at 0 ° C. with stirring. It was. The reaction mixture was stirred for an additional 18 hours, poured into ice, concentrated hydrochloric acid was added to pH 1 and the mixture was extracted multiple times with Et ₂ O. The organic phases were combined, washed with saturated aqueous NaHCO _{3 and} saturated aqueous NaCl, and dried over MgSO ₄ . The solvent was removed under reduced pressure, and the crude product was mixed with 1 dm ³ of toluene without further purification, 2 g of p-toluenesulfonic acid was added, and the mixture was refluxed for 2 hours. The reaction mixture was washed with 200 cm ³ of a saturated aqueous NaHCO ₃ solution and the solvent was removed under reduced pressure. The crude material was purified by filtration through 500 g of silica gel (hexane / CH ₂ Cl ₂ ) to give 42 g (90%) of 3 as a colorless oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 7.6 (m, 8H, arom.H), 6.5 (m, 1H, HC (3)), 3.4 (s , 2H, CH ₂ ), 2.1 (s, 3H, CH ₃ )
4). Dimethylbis (2-methyl-4-phenylindenyl) silane (4)
Solution obtained by dissolving and toluene 200 cm ³ free of H ₂ O and O _2, a 3 15 g (72.7 mmol) in a mixed solvent of THF and 10 cm ³ free of H ₂ O and O ₂ Was added 29 cm ³ (73 mmol) of a 2.5M solution of butyllithium in hexane at room temperature under an argon atmosphere and heated at 80 ° C. for 1 hour. The batch was subsequently cooled to 0 ° C. and 4.7 g (36.4 mmol) of dimethyldichlorosilane was added. The mixture was heated at 80 ° C. for 1 hour and then poured into 100 cm ³ of water. The mixture was extracted many times with Et ₂ O and the combined organic phases were dried over MgSO ₄ . The crude that remained after stripping the solvent was chromatographed on 300 g of silica gel (hexane / CH ₂ Cl ₂ ) to give 12.0 g (70%) of 4.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.10 to 7.70 (m, 16 H, arom. H), 6.80 (m, 2 H, HC (3)), 3.80 (s , 2H, H—C (1)), 2.20 (m, 6H, CH ₃ ), −0.20 (m, 6H, CH ₃ Si)
5. Dichloride rac- dimethylsilyl bis (2-methyl-4-phenyl-in-Denis Le) zirconium (5)
To a solution obtained by dissolving 6.0 g (12.9 mmol) of 4 in 100 cm ³ of toluene containing no H ₂ O and O ₂ , 10.6 cm ^{3 of a} 2.5 M solution of butyl lithium in hexane ( 26 mmol) was added at room temperature under an argon atmosphere and the mixture was refluxed for 3 hours. The dilithio salt suspension was cooled to −25 ° C. and 3.2 g (13.6 mmol) of zirconium tetrachloride was added. The batch was warmed to room temperature over 1 hour, stirred for an additional hour, and filtered through a G3 glass filter. The residue was extracted with 50 cm ³ of toluene, and the solvent was removed from the combined filtrates under reduced pressure by an oil pump. As a result, 9.0 g of metallocene in the form of a yellow powder was a mixture of racemic and meso forms (1: 1). As obtained. The pure racemate (5) was isolated by stirring the crude mixture several times with 20 cm ³ of methylene chloride in each case. The racemic compound remained as a yellow crystalline powder and the meso form was washed away. 2.74 g (33%) of pure racemate was obtained.

¹ H-NMR (300 MHz, CDCl ₃ ): 7.0 to 7.7 (m, 16H, arom.H), 6.9 (s, 2H, HC (3)), 2.2 (s, 6H, CH ₃ ), 1.3 (m, 6H, CH ₃ Si)
Molecular weight: 626M ⁺ , correct decomposition pattern
Example B
Rac-methylphenylsilanediylbis- (2-methyl-4-phenylindenyl) zirconium dichloride (7)
1. Methylphenylbisureido - (2-methyl-4-phenyl-indenyl) silane (6) and toluene 90ml free of H ₂ O and O _2, a mixed solvent of THF of 10ml free of H ₂ O and O ₂ 21 ml (52 mmol) of a 2.5M solution of butyllithium in hexane was added to a solution obtained by dissolving 10.3 g (50 mmol) of 3 in 3 at room temperature under an argon atmosphere. The mixture was heated at 80 ° C. for 1 hour and then cooled to 0 ° C. 4.8 g (25 mmol) of methylphenyldichlorosilane was added and stirring was continued overnight at room temperature. The precipitated LiCl was separated by filtration and the residual crude after stripping the solvent under reduced pressure was chromatographed on 300 g silica gel (hexane / CH ₂ Cl ₂ 9: 1) to give 4.6 g (35% 6) was obtained.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 7.8 (m, 16H, arom.H), 6.9 (m, 2H, HC (3)), 3.9 (m, 2H, H-C (1) ), 2.3 (m, 6H, CH 3), -0.1 (s, 3H, C H 3 Si)
2. Dichloride rac- methylphenyl silane diyl bis (2-methyl-4-Fe Niruindeniru) zirconium (7)
To a solution obtained by dissolving 2.3 g (4.4 mmol) of 6 in 25 ml of toluene without H ₂ O and O ₂ , 3.6 ml of a 2.5 M solution of butyllithium in hexane (8. 9 mmol) was added at room temperature under an argon atmosphere and the mixture was heated at 80 ° C. for 3 hours. The dilithiate suspension was cooled to -30 ° C and 1.1 g (4.5 mmol) of zirconium tetrachloride was added. The mixture was warmed to room temperature over 1 hour and stirred for an additional hour. After filtration through a G3 glass filter, the solvent was removed from the filtrate and the residue was recrystallized from 10 ml of methylene chloride to give 0.2 g of racemate 7 as orange crystals.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 8.2 (m, 21H, arom.H), 6.9 (m, 2H, HC (3)), 2.4 (s, _{3H, CH 3), 2.0 (} s, 3H, CH 3), 1.3 (s, 3H, CH 3 Si).

Mass spectrum: 690M ⁺ , correct decomposition pattern
Example C
Rac-Dimethylsilanediylbis (4-phenylindenyl) zirconium dichloride (12)
1. 3- (2-Phenylphenyl) propionic acid (8)
A solution obtained by dissolving 14 g (0.61 mmol) of sodium in 400 cm ³ of H ₂ O free EtOH was added 93 cm ³ (0.61 mmol) of diethyl malonate with 50 cm ³ of H ₂ O. A solution obtained by dissolving in EtOH not containing was dropped at room temperature. A solution obtained by dissolving 150 g (0.61 mmol) of 2-phenylbenzyl bromide in 200 cm ³ of EtOH containing no H ₂ O was then added dropwise, and the mixture was refluxed for 3 hours. A solution obtained by dissolving 102 g (1.83 mol) of KOH in 150 cm ³ of H ₂ O was added dropwise at room temperature, and the mixture was further refluxed for 4 hours. The solvent was removed under reduced pressure, H ₂ O was added to the residue until the residue was completely dissolved, and the mixture was acidified to pH 1 with concentrated hydrochloric acid. The resulting precipitate was filtered off with suction, dried and heated at 130 ° C. for 1 hour to give 112 g (81%) of 8 as a viscous oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 9.1 (s, 1 H, COOH), 6.9 to 7.5 (m, 9 H, arom. H), 2.3 to 3.0 (m, 4 H , 2CH ₂ ).
2. 4-Phenyl-1-indanone (9)
A solution obtained by dissolving 102 g (0.45 mol) of 8 in 37 cm ³ (0.5 mol) of thionyl chloride was stirred at room temperature for 18 hours. Excess thionyl chloride is removed at 10 mbar and, in each case, by repeated dissolution in 100 cm ³ of toluene, the sticky residue of thionyl chloride is removed from the oily residue and stripped at reduced pressure. It was.

200 cm ³ of toluene was mixed with the obtained acid chloride, and this was added dropwise at 10 ° C. to a suspension of 72 g (0.54 mol) of AlCl ₃ suspended in 1000 cm ³ of toluene. The reaction mixture was heated at 80 ° C. for 1 hour, poured into 1000 g of ice and acidified with concentrated hydrochloric acid to pH 1. The organic phase was separated and the aqueous phase was extracted 3 times with 200 cm ³ of Et ₂ O each. The organic phases were combined, washed with saturated aqueous NaHCO ₃ and NaCl and dried over MgSO ₄ to give 96 g (96%) of 9 which was used in the next reaction without further purification.

¹ H-NMR (1000 MHz, CDCl ₃ ): 6.9 to 7.5 (m, 8H, arom. H), 2.5 to 3.4 (m, 4H, 2CH ₂ ).
3. 7-Phenylindene (10)
To a solution obtained by dissolving 86 g (0.41 mol) of 9 in 300 cm ³ of THF / methanol (2: 1), 23 g (0.62 mol) of NaBH ₄ was added in small portions at 0 ° C. The reaction mixture was stirred at room temperature for 18 hours, poured into 300 g of ice, concentrated hydrochloric acid was added to pH 1 and the mixture was extracted many times with Et ₂ O. The combined organic phases were washed with saturated aqueous NaHCO _{3 and} saturated aqueous NaCl, dried over MgSO ₄ and the solvent removed under reduced pressure.

To the obtained crude product, 1000 cm ³ of toluene was mixed, 4.5 g of p-toluenesulfonic acid was added, the reaction mixture was refluxed for 2 hours using a water separator, and ³ times with 250 cm ³ of saturated aqueous NaHCO ₃ solution. Washed once and the solvent was removed under reduced pressure. Distillation at 96-108 ° C. at 0.1 mbar gave 33 g (41%) of 10 as a colorless oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.1 to 7.7 (m, 8H, arom.H), 6.9 and 6.5 (2m, 2H, CH), 3.5 (m, 2H, CH _2).
4). Dimethylbis (4-phenylindenyl) silane (11)
And toluene 100 cm ³ free of H ₂ O and O _2, to a solution obtained by dissolving 10 10 g (50 mmol) in a mixed solvent of THF and 5ml free of H ₂ O and O _2, butyl 18.7 cm ³ (50 mmol) of a 20% strength solution of lithium in toluene was added at room temperature and the mixture was heated at 80 ° C. for 2 hours. The yellow suspension was subsequently cooled to 0 ° C. and 3.2 g (25 mmol) of dimethyldichlorosilane was added. The reaction mixture was heated at 80 ° C. for an additional hour and then washed with 50 cm ³ of H ₂ O. The solvent was removed under reduced pressure, and the residue was recrystallized from heptane at −20 ° C. to give 6.7 g (62%) of 11 as colorless crystals (mp 109-110 ° C.).

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 7.7 (m, 18 H, arom. H, HC (3)), 6.8 (dd, 2 H, HC (2)) , 3.8 (m, 2H, H -C (1)), -0.2 (s, 6H, CH 3 Si).
5. Dichloride rac- dimethylsilanediylbis (4-phenyl indenyl) di Rukoniumu (12)
To a solution obtained by dissolving 6.6 g (16 mmol) of 11 in 70 cm ³ Et ₂ O without H ₂ O and O ₂ , 12 cm ³ (32 mmol) of a 20% strength solution of butyllithium in toluene was added. Was added at room temperature under an argon atmosphere and the mixture was refluxed for 3 hours. Remove the solvent under reduced pressure, add 50 ml of hexane without H ₂ O and O ₂ to the residue, filter through a G3 Schlenk glass filter, and wash with 50 ml of hexane without H ₂ O and O _2. And dried (0.1 mbar at room temperature).

To the suspension obtained by suspending 3.6 g (16 mmol) of zirconium tetrachloride in 80 cm ³ of methylene chloride, the dilithio salt was added at −78 ° C. and the mixture was stirred at room temperature with magnetic stirring for 18 hours. Warmed to. The batch was filtered through a G3 glass filter and the residue was extracted in several portions with a total of 200 cm ³ of methylene chloride. The solvent was removed from the combined filtrates under reduced pressure and recrystallized from methylene chloride / hexane (1: 1). 5.6 g of a mixture of racemate and meso form (1: 1) was obtained. Further recrystallization from methylene chloride yielded a racemic complex in the form of yellow crystals.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 7.8 (m, 22H, arom.H, and HC (3)), 6.1 (d, 2H, HC (2) ), 1.1 (s, 6H, CH ₃ Si).

Mass spectrum: 598M ⁺ , correct decomposition pattern
Example D
Rac-Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dichloride (17)
1. (±) -2- (2-Phenylbenzyl) butyric acid (13)
To a solution obtained by dissolving 23 g (1 mol) of sodium in 400 cm ₃ of EtOH without H ₂ O, 188 g (1 mol) of diethyl ethyl malonate was added with 100 cm ³ of H ₂ O free EtOH. The solution obtained by dissolving in was added dropwise at room temperature. Then, a solution obtained by dissolving 247 g (1 mol) of 2-phenylbenzyl bromide in 300 cm ³ of EtOH containing no H ₂ O was added dropwise, and the mixture was refluxed for 3 hours. A solution obtained by dissolving 170 g (3 mol) of KOH in 300 cm ³ of H ₂ O was added at room temperature, and the mixture was refluxed for a further 4 hours. The solvent was removed under reduced pressure, H ₂ O was added to the residue until the residue was completely dissolved, and the mixture was acidified to pH 1 with concentrated hydrochloric acid. The resulting precipitate was filtered off with suction, dried and heated at 130 ° C. for 1 hour to give 236 g (93%) of 13 as a viscous oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 10.3 (s, 1 H, COOH), 7.0 to 7.3 (m, 9 H, arom. H), 2.5 to 3.0 (m, 3 H, CH and _{CH 2), 1.5~1.9 (m,} 2H, CH 2), 0.9 (t, 3H, CH 3).
2. (±) -2-Ethyl-4-phenyl-1-indanone (14)
A solution obtained by dissolving 236 g (0.93 mol) of 13 in 81 cm ³ (1.2 mol) of thionyl chloride was stirred at room temperature for 18 hours. Excess thionyl chloride is removed at 10 mbar and, in each case, by repeated dissolution in 200 cm ³ of toluene, the sticky residue of thionyl chloride is removed from the oily residue and stripped at reduced pressure. It was.

The resulting mixture of toluene 400 cm ³ to the acid chloride, which was added dropwise at 10 ° C. the AlCl ₃ to a suspension in toluene of 2000 cm ³ of 133 g (1.0 mol). The reaction mixture was heated at 80 ° C. for 1 hour, poured into 2000 g of ice and acidified with concentrated hydrochloric acid to pH 1. The organic phase was separated and the aqueous phase was extracted 3 times with 200 cm ³ of Et ₂ O each. The organic phases were combined, washed with saturated aqueous NaHCO _{3 and} saturated aqueous NaCl, and dried over MgSO ₄ to give 187 g (85%) of 14 which was used in the next reaction without further purification.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 7.8 (m, 8H, arom.H), 3.1 to 3.4 (m, 1H, HC (3)), 2 .5-2.
9 (m, 2H, H- C (2) and H-C (3)), 1.3~2.0 (m, 2H, CH 2), 0.9 (t, 3H, CH 3).
3. 2-Ethyl-7-phenylindene (15)
To a solution obtained by dissolving 50 g (0.21 mol) of 14 in 600 cm ³ of THF / methanol (2: 1), 8 g (0.21 mol) of NaBH ₄ was added in portions at 0 ° C., The reaction mixture was stirred at room temperature for 18 hours, poured into 600 g of ice, concentrated hydrochloric acid was added to bring the pH to 1, and the mixture was extracted multiple times with Et ₂ O. The organic phases were combined, washed with saturated aqueous NaHCO _{3 and} saturated aqueous NaCl, and dried over MgSO ₄ .

The obtained crude product was mixed with 1000 cm ³ of toluene, 4.5 g of p-toluenesulfonic acid was added, the reaction mixture was refluxed for 2 hours using a water separator, and ³ times with 250 cm ³ of saturated aqueous NaHCO ₃ solution. Washed once and removed the solvent under reduced pressure. Distillation at 135 ° C. and 0.1 mbar gave 33 g of 15 as a colorless oil.

1H-NMR (100 MHz, CDCl ₃ ): 7.0 to 7.5 (m, 8H, arom.H), 6.5 (m, 1H, CH), 3.2 (m, 2H, CH ₂ ), _{2.5 (dq, 2H, CH 2} ), 1.1 (t, 3H, CH 3).
4). Dimethylbis (2-ethyl-4-phenylindenyl) silane (16)
And toluene 160cm ³ free of H ₂ O and O _2, to a solution obtained by dissolving 15 17 g (77 mmol) in a mixed solvent of THF in 8ml free of H ₂ O and O _2, butyl 29 cm ³ (77 mmol) of a 20% strength solution of lithium in toluene was added at room temperature and heated at 80 ° C. for 2 hours. The yellow suspension was subsequently cooled to 0 ° C. and 5 g (38 mmol) of dimethylchlorosilane was added. The reaction mixture was heated at 80 ° C. for an additional hour and then washed with 100 cm ³ of H ₂ O. The solvent was removed in vacuo and the residue was chromatographed on 200 g silica gel (hexane / CH ₂ Cl ₂ 9: 1) to give 9 g (47%) of 16 as a viscous oil.

^{1 H-NMR (100MHz, CDCl} 3): 6.97~7.4 (m, 16H, arom.H), 6.5 (m, 2H, H-C (3)), 3.7 (m, 2H, H-C (1) ), 2.4 (m, 4H, CH 2), 1.1 (t, 6H, CH 3), -0.1 (s, 6H, CH 3 Si).
5. Dichloride rac- dimethylsilanediylbis (2-ethyl-4-Fenirui Ndeniru) zirconium (17)
To a solution obtained by dissolving 5.6 g (11 mmol) of 16 in 50 cm ³ Et ₂ O without H ₂ O and O ₂ , 8.4 cm ³ of a 20% strength solution of butyllithium in toluene was added. At room temperature under an argon atmosphere and the mixture was refluxed for 3 hours. The solvent was removed under reduced pressure, and the residue was mixed with 50 ml of hexane containing no H ₂ O and O ₂ , filtered through a G3 Schlenk glass filter, and 50 ml of hexane containing no H ₂ O and O _2. And dried (0.1 mbar, room temperature).

To a suspension of 2.5 g (11 mmol) of zirconium tetrachloride in 50 cm ³ of methylene chloride, the dilithio salt was added at −78 ° C. and the mixture was allowed to room temperature over 18 hours with magnetic stirring. Warmed up. The batch was filtered through a G3 glass filter and the residue was then extracted using a total of 100 cm ³ of methylene chloride in small portions. The solvent was removed from the combined filtrates under reduced pressure, and recrystallization from toluene / hexane (1: 1) gave 2 g (27%) of a mixture of racemic and meso forms (1: 1). Further recrystallization from toluene gave a racemic complex in the form of yellow crystals.

¹ H-NMR (100 MHz, CDCl ₃ ): 6.8 to 7.7 (m, 16H, arom.H), 6.6 (m, 2H, HC (3)), 2.3 to 3. _{9 (m, 4H, CH 2} ), 1.0~1.4 (m, 12H, CH 3 and CH ₃ Si).

Mass spectrum: 654 ⁺ , correct decomposition pattern
Example E
Rac-Dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride (24)
1. 2- (1-Naphthyl) toluene (18)
13.9 g (0.57 mol) of magnesium shavings were immersed in 150 ml of Et ₂ O without H ₂ O and the Grignard reaction was initiated with 5 g of 2-bromotoluene and a few pieces of iodine. Next, a solution obtained by dissolving 93 g (0.57 mol) of 1-bromotoluene in 150 ml of Et ₂ O without H ₂ O was added dropwise at such a rate that the reaction mixture kept boiling. . After the addition was complete, boiling was continued until the magnesium was completely reacted.

The Grignard solution was then dissolved in a solution obtained by dissolving 118 g (0.57 mol) of 1-bromonaphthalene and 3.5 g of bis (triphenylphosphine) nickel dichloride in 800 cm ³ of toluene. It was dripped at such a speed that the temperature did not exceed 50 ° C. The mixture was further refluxed for 3 hours, 500 ml of 10% strength hydrochloric acid was added, the organic phase was separated, and the solvent was removed from the organic phase under reduced pressure. Filtration through silica gel (hexane) gave 115 g (92%) of 18 as a colorless oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.2 to 8.0 (m, 11H, arom. H), 2.0 (s, 3H, CH ₃ ).
2. 2- (1-Naphtyl) benzyl bromide (19)
114 g (0.52 mol) of 18 and 103 g (0.58 mol) of N-bromo-succinimide are dissolved in 2000 cm ³ of tetrachloromethane at room temperature, and 3 g of azobisisobutyronitrile is added. The mixture was refluxed for 4 hours. The precipitated succinimide is filtered off, the solvent is removed under reduced pressure, and the residue is purified by filtration through 1000 g of silica gel (hexane / methylene chloride 9: 1) to give 141 g (82%) of 19 colorless. As an oil.

¹ H-NMR (100 MHZ, CDCl ₃ ): 7.1-8.0 (m, 11H, arom. H), 4.2 (q, 2H, CH ₂ Br).
3. (±) -2- (2- (1-naphthyl) benzyl) propionic acid (20)
To a solution obtained by dissolving 10 g (0.43 mmol) of sodium in 100 cm ³ of EtOH without H ₂ O, 75 g (0.43 mmol) of diethyl methylmalonate was added to 50 cm of H ₂ O. ^A solution obtained by dissolving in ³ EtOH was added dropwise at room temperature. Subsequently, a solution obtained by dissolving 140 g (0.43 mmol) of 2-phenylbenzyl bromide in 200 cm ³ of EtOH containing no H ₂ O was added dropwise, and the mixture was refluxed for 3 hours. A solution obtained 85g of KOH (1.3 mol) dissolved in H ₂ O in 100 cm ³ at room temperature to reflux The mixture further 4 hours. The solvent was removed under reduced pressure, H ₂ O was added to the residue until the residue was completely dissolved, and the mixture was acidified to pH 1 with concentrated hydrochloric acid. The resulting precipitate was filtered off with suction, dried and heated at 130 ° C. for 1 hour to give 96 g (77%) of 20 as a viscous oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 10.1 (s, 1 H, COOH), 6.9 to 8.0 (m, 11 H, arom. H), 2.3 to 3.0 (m, 3 H , CH ₂ and CH), 0.8 (d, 3H, CH ₃ ).
4). (±) -2-Methyl-4- (1-naphthyl) -1-indanone (21)
A solution obtained by dissolving 96 g (0.33 mol) of 20 in 37 cm ³ (0.5 mol) of thionyl chloride was stirred at room temperature for 18 hours. Excess thionyl chloride was removed at 10 mbar, and in each case the thionyl chloride adhesive residue was removed from the oily residue by repeated dissolution in 100 cm ³ of toluene and stripping at reduced pressure. .

200 cm ³ of toluene was mixed with the obtained acid chloride, and this was added dropwise at 10 ° C. to a suspension of 44 g (0.33 mol) of AlCl ₃ suspended in 1000 cm ³ of toluene. After completion of the addition, the mixture was heated at 80 ° C. for 3 hours, poured into 1000 g of ice and acidified to pH 1 with concentrated hydrochloric acid. The organic phase was separated and the aqueous phase was extracted three times with 200 cm ³ each of methylene chloride. The organic phases were combined, washed with saturated aqueous NaHCO _{3 and} saturated aqueous NaCl, and dried over MgSO ₄ . Chromatography on 1000 g silica gel (hexane / methylene chloride) gave 12 g (13%) of 21.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.3-8.0 (m, 10H, arom.H), 2.2-3.2 (m, 3H, CH ₂ and CH), _{2 (d, 3H, CH 3} ).
5. 2-Methyl-7- (1-naphthyl) indene (22)
To a solution obtained by dissolving 12 g (44 mmol) of 21 in 100 cm ³ of THF / methanol (2: 1), 1.3 g (33 mmol) of NaBH ₄ was added at 0 ° C., and this reaction mixture was added. Was stirred at room temperature for 18 hours, poured into 100 g of ice, acidified to pH 1 with concentrated hydrochloric acid and extracted multiple times with Et ₂ O. The organic phases were combined, washed with saturated aqueous NaHCO _{3 and} saturated aqueous NaCl, and dried over MgSO ₄ .

The crude product thus obtained was mixed with 200 cm ³ of toluene, 0.5 g of p-toluenesulfonic acid was added, the reaction mixture was refluxed for 2 hours using a water separator, and 50 cm ³ of a saturated aqueous NaHCO ₃ solution. And the solvent was removed under reduced pressure. Filtration through 200 g of silica gel (hexane / methylene chloride) gave 10 g (86%) of 22 as a colorless oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 8.0 (m, 10H, arom.H), 6.6 (m, 1H, CH), 3.0 (m, 2H, CH ₂ ) , 2.0 (m, 3H, CH ₃ ).
6). Dimethylbis (2-methyl-4- (1-naphthyl) indenyl) silane (23 )
And toluene 100 cm ³ free of H ₂ O and O _2, a solution obtained by dissolving 22 10 g (38 mmol) in a mixed solvent of THF and 5ml free of H ₂ O and O _2, 14.4 cm ³ (50 mmol) of a 20% strength solution of butyllithium in toluene was added at room temperature and the mixture was heated at 80 ° C. for 2 hours. The yellow suspension was cooled to 0 ° C. and 2.5 g (19 mmol) of dimethyldichlorosilane was added. The reaction mixture was heated at 80 ° C. for an additional hour and then washed with 50 cm ³ of H ₂ O. The solvent was removed under reduced pressure and the residue was recrystallized from heptane at −20 ° C. to give 8.2 g (75%) of 23 as colorless crystals.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.2-8.1 (m, 20H, arom.H), 6.4 (m, 2H, HC (3)), 4.0 (m, 2H, H-C (1) ), -0.1 (s, 6H, CH 3 Si).
7). Dichloride rac- dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl) zirconium (24)
To a solution obtained by dissolving 8.0 g (14 mmol) of 23 in 70 cm ³ of Et ₂ O without H ₂ O and O ₂ , 10.5 cm ³ of a 20% strength solution of butyllithium in toluene was added. At room temperature under an argon atmosphere and the mixture was refluxed for 3 hours. The solvent was removed under reduced pressure, and the residue was mixed with 50 ml of hexane containing no H ₂ O and O ₂ , filtered through a G3 Schlenk glass filter, and 50 ml of hexane containing no H ₂ O and O _2. And dried (0.1 mbar, room temperature).

To a suspension of 3.2 g (14 mmol) of zirconium tetrachloride in 80 cm ³ of methylene chloride, the dilithio salt was added at −78 ° C., and the mixture was stirred at room temperature for 18 hours with magnetic stirring. Warmed to. The batch was filtered through a G3 glass filter and the residue was then extracted using a total of 400 cm ³ of methylene chloride in several portions. The solvent was removed from the combined filtrates under reduced pressure, and recrystallization from methylene chloride gave 1.5 g (15%) of a racemic and meso mixture (1: 1). Further recrystallization from methylene chloride yielded a racemic complex in the form of yellow crystals.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 8.0 (m, 22H, arom.H), 6, 5 (s, 2H, HC (3)), 2.2 (s, 6H, CH ₃ ), 1.3 (s, 6H, CH ₃ Si).

Mass spectrum: 729 ⁺ , correct decomposition pattern
Example F
Rac-Dimethylsilanediylbis (2-methyl-4- (2-naphthyl) indenyl) zirconium dichloride (31)
1. 2- (2-Naphthyl) toluene (25)
14 g (0.57 mol) of magnesium shavings were immersed in 150 ml of Et ₂ O without H ₂ O and the Grignard reaction was initiated with 5 g of 2-bromotoluene and a few pieces of iodine. A solution obtained by dissolving 95 g (0.58 mol) of 1-bromotoluene in 450 ml of Et ₂ O without H ₂ O was then added dropwise at such a rate that the reaction mixture kept boiling. . After the addition was complete, boiling was continued until the magnesium was completely reacted.

The Grignard solution was then added to a solution obtained by dissolving 120 g (0.57 mol) of 2-bromonaphthalene and 3.5 g of bis (triphenylphosphine) nickel dichloride in 800 cm ³ of toluene. The dropwise addition was performed at such a rate that the temperature did not exceed 50 ° C. The mixture was further refluxed for 3 hours, 500 ml of 10% strength hydrochloric acid was added, the organic phase was separated, and the solvent was removed from the organic phase under reduced pressure. Filtration through silica gel (hexane) gave 107 g (87%) of 25 as a colorless oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 7.9 (m, 11H, arom. H), 1.9 (s, 3H, CH ₃ ).
2. 2- (2-Naphthyl) benzyl bromide (26)
105 g (0.48 mol) of 25 and 90 g (0.5 mol) of N-bromo-succinimide are dissolved in 2000 cm ³ of tetrachloromethane at room temperature, and 3 g of azobisisobutyronitrile is added. The mixture was refluxed for 4 hours. The precipitated succinimide was filtered off, the solvent was removed at reduced pressure, and the residue was purified by filtration through 1000 g of silica gel (hexane / methylene chloride 9: 1) to give 112 g (79%) of 26 colorless. As an oil.

^{1 H-NMR (100MHZ, CDCl} 3): 6.9~8.0 (m, 11H, arom.H), 4.1 (s, 2H, CH 2 Br).
3. (±) -2- (2- (2-naphthyl) benzyl) propionic acid (27)
To a solution obtained by dissolving 8.5 g (0.37 mmol) of sodium in 100 cm ³ of EtOH without H ₂ O, 70 g (0.37 mmol) of diethyl methylmalonate was added with H ₂ O. A solution obtained by dissolving in 50 cm ³ of EtOH not contained was dropped at room temperature. Next, a solution obtained by dissolving 110 g (0.37 mmol) of 26 in 200 cm ³ of EtOH containing no H ₂ O was added dropwise, and the mixture was refluxed for 3 hours. A solution obtained by dissolving 62 g (1.1 mol) of KOH in 100 cm ³ of H ₂ O was added at room temperature and the mixture was refluxed for a further 4 hours. The solvent was removed under reduced pressure, H ₂ O was added to the residue until the residue was completely dissolved, and the mixture was acidified to pH 1 with concentrated hydrochloric acid. The resulting precipitate was filtered off with suction, dried and heated at 130 ° C. for 1 h to give 96 g (84%) of 27 as a viscous oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 10.9 (s, 1 H, COOH), 7.0 to 8.1 (m, 11 H, arom. H), 2.3 to 3.0 (m, 3 H , CH ₂ and CH), 1.0 (d, 3H, CH ₃ ).
4). (±) -2-Methyl-4- (2-naphthyl) -1-indanone (28)
A solution obtained by dissolving 89 g (0.31 mol) of 27 in 37 cm ³ (0.5 mol) of thionyl chloride was stirred at room temperature for 18 hours. Excess thionyl chloride was removed at 10 mbar, and in each case the thionyl chloride adhesive residue was removed from the oily residue by repeated dissolution in 100 cm ³ of toluene and stripping at reduced pressure. .

200 cm ³ of toluene was mixed with the obtained acid chloride, and this was added dropwise at 10 ° C. to a suspension of 44 g (0.33 mol) of AlCl ₃ suspended in 1000 cm ³ of toluene. After completion of the addition, the mixture was heated at 80 ° C. for 3 hours, poured into 1000 g of ice and acidified with concentrated hydrochloric acid to pH 1. The organic phase was separated and the aqueous phase was extracted three times with 200 cm ³ each of methylene chloride. The organic phases were combined, washed with saturated aqueous NaHCO _{3 and} saturated aqueous NaCl, and dried over MgSO ₄ . Chromatography on 100 g silica gel (hexane / AeOEt) gave 27 g (33%) of 28.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.1-8.0 (m, 10H, arom.H), 2.2-3.3 (m, 3H, CH ₂ and CH), _{1 (d, 3H, CH 3} ).
5. 2-Methyl-7- (2-naphthyl) indene (29)
To a solution obtained by dissolving 27 g (100 mmol) of 28 in 200 cm ³ of THF / methanol (2: 1), 3.8 g (100 mmol) of NaBH ₄ was added at 0 ° C. Was stirred at room temperature for 18 hours, poured into 100 g of ice, acidified to pH 1 with concentrated hydrochloric acid and the mixture was extracted several times with Et ₂ O. The organic phases were combined, washed with saturated aqueous NaHCO _{3 and} saturated aqueous NaCl, and dried over MgSO ₄ .

The crude product thus obtained was mixed with 500 cm ³ of toluene, 1.5 g of p-toluenesulfonic acid was added, the reaction mixture was refluxed for 2 hours using a water separator, and 50 cm ³ of a saturated aqueous NaHCO ₃ solution. And the solvent was removed under reduced pressure. Filtration through 200 g of silica gel (hexane / methylene chloride) gave 18.4 g (72%) of 29 as a colorless oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 8.0 (m, 10H, arom.H), 6.6 (m, 1H, CH), 3.0 (m, 2H, CH ₂ ) , 2.0 (m, 3H, CH ₃ ).
6). Dimethylbis (2-methyl-4- (2-naphthyl) indenyl) silane (30 )
And toluene 70cm ³ free of H ₂ O and O _2, a solution obtained by dissolving 29 18 g (70 mmol) in a mixed solvent of THF in 4ml free of H ₂ O and O _2, 26 cm ³ (70 mmol) of a 20% strength solution of butyl lithium in toluene was added at room temperature and the mixture was heated at 80 ° C. for 2 hours. The yellow suspension was cooled to 0 ° C. and 4.5 g (35 mmol) of dimethyldichlorosilane was added. The reaction mixture was heated at 80 ° C. for an additional hour and then washed with 50 cm ³ of H ₂ O. The solvent was removed under reduced pressure and the residue was recrystallized from heptane at −20 ° C. to give 10.8 g (54%) of 30 as colorless crystals.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 8.1 (m, 20H, arom.H), 6.4 (m, 2H, HC (3)), 4.0 (m, 2H, H-C (1) ), -0.1 (s, 6H, CH 3 Si).
7). Dichloride rac- dimethylsilanediylbis (2-methyl-4- (2-naphthyl) indenyl) zirconium (31)
To a solution obtained by dissolving 10.5 g (18 mmol) of 30 in 70 cm ³ of Et ₂ O without H ₂ O and O ₂ , 13.6 cm ³ of a 20% strength solution of butyllithium in toluene was added. At room temperature under an argon atmosphere and the mixture was refluxed for 3 hours. The solvent was removed under reduced pressure, and the residue was mixed with 50 ml of hexane containing no H ₂ O and O ₂ , filtered through a G3 Schlenk glass filter, and 50 ml of hexane containing no H ₂ O and O _2. And dried (0.1 mbar, room temperature).

To a suspension of 4.2 g (18 mmol) of zirconium tetrachloride in 80 cm ³ of methylene chloride, the dilithio salt was added at −78 ° C. and the mixture was allowed to room temperature over 18 hours with magnetic stirring. Warmed up. The batch was filtered through a G3 glass filter and the residue was then extracted using a total of 400 cm ³ of methylene chloride in several portions. Solvents were removed from the combined filtrates under reduced pressure, and recrystallization from methylene chloride gave 3.1 g (23%) of a racemic and meso mixture (1: 1). Further recrystallization from methylene chloride yielded a racemic complex in the form of yellow crystals.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 8.0 (m, 22H, arom.H), 6.9 (s, 2H, HC (3)), 2.2 (s, _{6H, CH 3), 1.3 (} s, 6H, CH 3 Si).
Example G
Rac-ethanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride (33)
1. 1,2-bis (2-methyl-4-phenylindenyl) ethane (32)
To a solution obtained by dissolving 50 g (0.24 mol) of 3 in 500 ml of THF was added 90 cm ³ (0.24 mol) of a 20% strength solution of butyllithium in toluene. The mixture was stirred at 60 ° C. for 2 hours, cooled to −78 ° C., 22.5 g (0.12 mol) dibromoethane was added and warmed to room temperature over 18 hours. The reaction mixture was washed with 50 cm ³ H ₂ O, the solvent was removed under reduced pressure, and the resulting residue was chromatographed on 500 g silica gel (hexane / methylene chloride 9: 1) to give 2.5 g (5 %) Of 32 was obtained as a yellow oil. This oil gradually solidified at -20 ° C.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 8.1 (m, 20H, arom.H), 6.4 (m, 2H, HC (3)), 4.0 (m, 2H, H-C (1) ), -0.1 (s, 6H, CH 3 Si).
2. Rac-ethanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride (33)
A solution obtained by dissolving 2.3 g (5 mmol) of 32 in 20 ml of Et ₂ O without H ₂ O and O ₂ was dissolved in 4 cm ³ (10 mmol) of a 20% strength solution of butyllithium in toluene. ) Was added at room temperature under an argon atmosphere and the mixture was refluxed for 3 hours. The solvent was removed under reduced pressure, the residue was mixed with 30 ml of hexane without H ₂ O and O ₂ , filtered through a G3 Schlenk glass filter, and washed with 30 ml of hexane without H ₂ O and O _2. And dried (0.1 mbar, room temperature).

To a suspension obtained by suspending 1.2 g (5 mmol) of zirconium tetrachloride in 30 cm ³ of methylene chloride, the dilithio salt is added at −78 ° C. and the mixture is stirred for 18 hours with magnetic stirring. Warmed to room temperature. The batch was filtered through a G3 glass filter and a total of 100 cm ³ of methylene chloride was divided into several portions to extract the residue. The solvent was removed from the combined filtrates under reduced pressure, and recrystallization from methylene chloride / hexane gave 0.5 g (18%) of a racemic and meso mixture (1: 1). Further recrystallization from toluene gave a racemic complex in the form of yellow crystals.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 to 7.7 (m, 16H, arom.H), 6.6 (m, 2H, HC (3)), 3.4 to 4. _{1 (m, 4H, H 2} C-CH 2), 2.1 (s, 6H, CH 3).

Mass spectrum: 598 ⁺ , correct decomposition pattern
Example H
Me ₂ Si (2-Me-2-Ph-indenyl) ₂ ZrMe [BPh ₄ ] (35)
1. rac- dimethylsilanediylbis (2-methyl-4-phenyl-in-Denis Le) dimethyl zirconium (34)
To a solution obtained by dissolving 0.5 g (0.8 mmol) of rac-5 in 10 cm ³ of Et ₂ O without H ₂ O and O ₂ was added 1.6 M of methyllithium in Et ₂ O. 1 cm ³ of the (1.6 mmol) solution was added at −30 ° C. and the mixture was stirred at 0 ° C. for 1 hour. The solvent was removed under reduced pressure and the residue was mixed with 20 cm ³ hexane without H ₂ O and O ₂ and filtered through a G3 glass filter to give 0.34 g (72%) of 34.

Mass spectrum: 588M ⁺ , correct decomposition pattern2. Me ₂ Si (2-Me-4-Ph-indenyl) ₂ ZrMe [BPh ₄ ] ( 35 )
To a solution obtained by dissolving 0.25 g of tributylammonium tetraphenylborate in 30 cm ³ of toluene, 0.2 g (0.3 mmol) of 34 was added at 0 ° C. The mixture was warmed to 50 ° C. with stirring and stirred at this temperature for 15 minutes. A small amount of this solution was used to study the polymerization.
Example 1
A 16 dm ³ volume dried reactor was first flushed with nitrogen and then with propylene and charged with 10 dm ³ of liquid propylene. 30 cm ³ of a toluene solution of methylaluminoxane was added and the batch was stirred at 30 ° C. for 15 minutes.

In parallel to this, and reacted by dissolving rac-5 of 1.1mg in a toluene solution of methylaluminoxane 20 cm ³ (27 mmol of Al), to stand for 15 minutes. The solution was then introduced into the reactor, heated to a polymerization temperature of 50 ° C. (4 ° C./min) and held at 50 ° C. for 1 hour by cooling the polymerization system. The polymerization was stopped by adding 20 cm ³ of isopropanol. Excess monomer was removed in gaseous form and the polymer was dried under reduced pressure to yield 0.9 kg of polypropylene. In the reactor, thin deposits were observed on the inner wall and the stirrer. The catalyst activity was 818 kg of PP per (metallocene 1 g × 1 hour). VI = 905 cm ³ / g; m. p. II = 98.8%; mmmm = 95.4%; M _w = 1,100,000 g / mol; M _w / M _n = 2.5
Example 2
The polymerization of Example 1 was repeated except that the catalyst used was 0.9 mg rac-5 and the polymerization temperature was 70 ° C. 1.4 kg of polypropylene was obtained. In the reactor, thick deposits were observed on the inner wall and the stirrer. The catalytic activity was 1,555 kg of PP per (metallocene 1 g × 1 hour). VI = 719 cm ³ / g; m. p. = 157.7 ° C.
Example 3
A 22 cm ³ (49 mmol Al) suspension of “MAO on SiO ₂ ” was introduced into a G3 Schlenk glass filter under an argon atmosphere and 4.5 mg of rac-5 was dissolved in 10 cm ³ of toluene. The resulting solution (7.2 micromolar Zr) was added. The reaction mixture was stirred at room temperature for 30 minutes, at which time the color of the reaction mixture turned red and gradually faded. The mixture was filtered and the resulting solid was washed 3 times with 10 cm ³ of hexane. The filter residue containing hexane was suspended again in 20 cm ³ of hexane, and the polymerization was examined.

In parallel, a 16 dm ³ volume dried reactor was first flushed with nitrogen and then with propylene and charged with 10 dm ³ of liquid propylene. 3 cm ³ of triisobutylaluminum (high purity, 12 mmol) was diluted with 30 cm ³ of hexane and introduced into the reactor, and the batch was stirred at 30 ° C. for 15 minutes. The catalyst suspension was then introduced into the reactor, heated to a polymerization temperature of 50 ° C. (4 ° C./min) and held at 50 ° C. for 1 hour by cooling the polymerization system. The polymerization was stopped by adding 20 cm ³ of isopropanol. 300 g of polypropylene powder was obtained. In the reactor, no deposits were observed on the inner wall and the stirrer. The catalyst activity was 67 kg PP per (metallocene 1 g × 1 hour). VI = 1380 cm ³ / g; m. p. = 156 ° C
Example 4
The support described in Example 3 except that 13 cm ³ (29 mmol of Al) suspension of “MAO on SiO ₂ ” and 1.8 mg of rac-5 (2.9 μmol Zr) were used. The synthesis of the catalyst system was repeated.

In the same manner as in Example 3, polymerization was carried out at 70 ° C. 420 g of polypropylene powder was obtained. In the reactor, no deposits were observed on the inner wall and the stirrer. The catalytic activity was 233 kg of PP per (metallocene 1 g × 1 hour). ^{VI = 787cm 3 / g; m} . p. = 149.5 ° C.
Example 5
A suspension of “MAO on SiO ₂ ” 150 cm ³ (335 mmol Al) and 44.2 mg rac-5 (7.03 μmol Zr) was used and the reaction mixture was stirred at room temperature for 60 min. Except for this, the synthesis of the supported catalyst system described in Example 3 was repeated. The solid was then filtered off and washed 3 times with 50 cm ³ of hexane. When the filter residue containing hexane was dried under reduced pressure, a free-flowing pale pink powder was obtained. 33.3 g of dry supported catalyst was obtained.

During the polymerization, 2.98 g (4 mg = 6.3 μmol of Zr) of this dry catalyst was resuspended in 20 cm ³ of hexane.
Polymerization was carried out at 70 ° C. in the same manner as in Example 3. 1.05 kg of polypropylene powder was obtained. In the reactor, no deposits were observed on the inner wall and the stirrer. The catalytic activity was 263 kg of PP per (metallocene 1 g × 1 hour). VI = 944 cm ³ / g; m. p. = 156 ° C.
Example 6
A 1.5 dm ³ volume dry reactor was flushed with nitrogen and 750 cm ³ benzine fraction at 20 ° C. (boiling range 100-120 ° C., aromatics removed (“Exxsol 100/120”) ] Was prepared. The reactor gas space was then flushed to purge nitrogen by introducing 8 bar of propylene, releasing the pressure, and repeating this procedure four times. Then 3.75 cm ^{3 of} methylaluminoxane in toluene (10% by weight of MAO) was added. The reactor contents were heated to 30 ° C. with stirring for 15 minutes and the total pressure was set to 8 bar by adding propylene at a stirring speed of 500 rpm.

In parallel with this, 0.1 mg of rac-5 was dissolved in 1.25 cm ^{3 of a} solution of methylaluminoxane in toluene and allowed to stand for 15 minutes for complete reaction. The solution was then introduced into the reactor and the polymerization system was heated to a temperature of 50 ° C. and held at this temperature for 1 hour by appropriate cooling. During this time, the pressure was maintained at 8 bar by appropriately feeding propylene, the reaction was stopped by adding 2 cm ³ of isopropanol, the resulting polymer was filtered off and dried at reduced pressure.

16 g of polypropylene was obtained. In the reactor, deposits were observed on the inner wall and the stirrer. The catalytic activity was 20 kg PP per (metallocene 1 g × 1 hour × 1 bar). VI = 833 cm ³ / g; m. p. = 159 ° C.
Example 7
The polymerization described in Example 6 was repeated except that the polymerization temperature was 60 ° C.

35 g of polypropylene was obtained. In the reactor, deposits were observed on the inner wall and the stirrer. The catalytic activity (CTY _red ) was 44 kg PP per (metallocene 1 g × 1 hour × 1 bar). VI = 484 cm ³ / g; m. p. = 159 ° C.
Example 8
The polymerization described in Example 6 was repeated except that the polymerization temperature was 70 ° C.

88 g of polypropylene was obtained. In the reactor, deposits were observed on the inner wall and the stirrer. The catalytic activity (CTY _red ) was 110 kg PP per (metallocene 1 g × 1 hour × 1 bar). ^{VI = 414cm 3 / g; m} . p. = 159 ° C.
Examples 9-12
The procedure is as described in Example 2. However, hydrogen was metered before filling with liquid propylene.
Example H ₂ activity of dm ² metallocene [(metallocene 1 g VI
(S.t.) × kg of PP per hour)] [cm ³ / g]
9 1.5 1640 495
10 3 1590 212
11 4.5 1720 142
12 200 1580 17
Examples 9-12 show good hydrogen utilization of the metallocenes according to the present invention. Molecular weight adjustment to the wax region is possible (see Example 12).
Example 13
The procedure is as described in Example 3. However, before adding the catalyst, 0.2 bar of hydrogen was introduced into the reactor and the polymerization temperature was 60 ° C. However, ethylene was metered in at a uniform rate during the polymerization. A total of 12 g of ethylene was introduced into the reactor. 0.4 kg of ethylene copolymer was obtained. The activity of the metallocene was 88 kg of copolymer per (metallocene 1 g × 1 hour). The ethylene content of the polymer was 2.4% by weight, and ethylene was mainly incorporated as an isolated unit. VI = 200 cm ³ / g; melting point 143 ° C.
Example 14
The procedure is as described in Example 13. However, a total of 34 g of ethylene was introduced during the polymerization. 0.38 kg of ethylene-propylene copolymer containing 7% by weight of ethylene was obtained. VI = 120 cm ³ ; melting point 121 ° C.
Example 15
The procedure is as described in Example 4. However, 4 g of ethylene was introduced during the polymerization and 0.1 bar of hydrogen was introduced before the polymerization. 0.52 kg of ethylene-propylene copolymer was obtained. The activity of metallocene was 286 kg of copolymer per (metallocene 1 g × 1 hour). The ethylene content of the polymer was 6.1% by weight and most of the ethylene was incorporated as an independent unit. VI = 150 cm ³ / g; melting point 116 ° C.
Example 16
A 150 dm ³ volume dry reactor was flushed with nitrogen and charged with 80 dm ³ benzine fraction (boiling range 100-120 ° C., aromatics removed) at 20 ° C. The reactor gas space was then flushed to purge nitrogen by introducing 2 bar of propylene, releasing the pressure, and repeating this procedure four times. After the addition of 50 liters of liquid propylene, 64 cm ^{3 of} methylaluminoxane in toluene (corresponding to 100 mmol of Al, molecular weight 1080 g / mol according to freezing point depression method) was added and the reactor contents were heated to 50 ° C. . By introducing hydrogen, the reactor gas space had a hydrogen content of 2.0%, and this hydrogen content was kept constant by continued introduction during the first polymerization step.

9.8 mg of rac-7 was dissolved in 32 ml of a toluene solution of methylaluminoxane (corresponding to 50 mmol of Al), and after standing for 15 minutes, this solution was introduced into the reactor. In the first polymerization step, polymerization was carried out at 50 ° C. for 5 hours. The gaseous component was then removed at a reactor pressure of 3 bar and 2000 g of ethylene gas was fed. During this operation, the reactor pressure increased to 8 bar and the polymerization was continued at 40 ° C. for a further 14 hours, after which the reaction was stopped with CO ₂ gas.

18.6 kg of block copolymer was obtained. The activity of the metallocene was 99.9 kg of copolymer per (metallocene 1 g × 1 hour). VI = 230 cm ³ / g; MFI (230/5) = 11 dg / min, MFI (230 / 2.16) = 3.7 dg / min; melting point of polymer in the first polymerization step: 159 ° C .; second polymerization Glass transition temperature of the polymer in the process: -38 ° C. This block copolymer contained 5% ethylene. According to the fractionation of the product, composition: 69% by weight of the homopolymer and 31% by weight of the copolymer is obtained, said copolymer having a ethylene content of 15 wt% In this case, the average C ₂ block length 2. 2.
Example 16a
The procedure is as described in Example 16.

3 mg of rac-24 was dissolved in 32 ml of a toluene solution of methylaluminoxane (corresponding to 50 mmol of Al) and allowed to stand for 15 minutes and then introduced into the reactor. In the first polymerization step, polymerization was carried out at 50 ° C. for 2.5 hours. Gaseous components were removed at a reactor pressure of 3 bar and 3000 g of ethylene was fed. During this operation, the reactor pressure increased to 8 bar and polymerization was continued at 40 ° C. for a further 8 hours, after which the reaction was stopped with CO ₂ gas.

16.5 kg of block copolymer was obtained. The activity of the metallocene was 524 kg of copolymer per (metallocene 1 g × 1 hour). VI = 480 cm ³ / g; MFI (230/5) = 2 dg / min; melting point of polymer in the first polymerization step: 162 ° C .; glass transition temperature of polymer in the second polymerization step: −54 ° C. This block copolymer contained 15% ethylene.
Example 17
The procedure is as described in Example 1. However, 12.5 mg of metallocene rac-7 was used. 1.5 kg of polypropylene was obtained. The activity of the metallocene was 120 kg of PP per (metallocene 1 g × 1 hour). VI = 1050 cm ³ / g; melting point 159 ° C.
Example 18
The procedure is as described in Example 2. However, 4.1 mg of metallocene rac-7 was used. 1.3 kg of polypropylene was obtained. The activity of metallocene was 317 kg of PP per (metallocene 1 g × 1 hour). VI = 555 cm ³ / g; melting point 157 ° C.
Comparative Example A
The procedure is as described in Example 1. However, 12.5 mg of rac-phenyl (methyl) silanediylbis (2-methyl-1-indenyl) zirconium dichloride was used. 1.35 kg of polypropylene was obtained. The activity of metallocene was 108 kg PP per (metallocene 1 g × 1 hour). VI = 1050 cm ³ / g; melting point 149 ° C.
Comparative Example B
The procedure is as described in Example 1. However, 12.5 mg of rac-phenyl (methyl) silanediylbis (1-indenyl) zirconium dichloride was used. 0.28 kg of polypropylene was obtained. The activity of metallocene was 22.4 kg of PP per (metallocene 1 g × 1 hour). VI = 74 cm ³ / g; melting point 141 ° C.
Example 19
The procedure is as described in Example 1. However, 3.3 mg of rac-24 was used. 0.78 kg of polypropylene was obtained. The activity of metallocene was 237 kg of PP per (metallocene 1 g × 1 hour). VI = 1700 cm ³ / g; mp 163 ° C .; M _w = 2.1 × 10 ⁶ g / mol; MFI (230 / 21.6) = 1 dg / min; M _w / M _n = 2.1.
Example 19a
The procedure is as described in Example 2. However, 1.0 mg of rac-24 was used. 1.2 kg of polypropylene was obtained. The activity of the metallocene was 1200 kg PP per (metallocene 1 g × 1 hour). VI = 1100 cm ³ / g; melting point 161 ° C.
Example 20
The procedure is as described in Example 1. However, the polymerization temperature was 40 ° C., and 6.0 mg of rac-17 was used. 1.95 kg of polypropylene was obtained. The activity of metallocene was 325 kg of PP per (metallocene 1 g × 1 hour). VI = 1320 cm ³ / g; melting point 162 ° C .; M _w = 1.79 × 10 ⁶ g / mol; M _w / M _n = 2.3.
Comparative Example C
The procedure is as described in Example 20. However, rac-dimethylsilanediylbis (2-ethyl-1-indenyl) zirconium dichloride, which is a conventional metallocene, was used. 0.374 kg of polypropylene was obtained. The activity of metallocene was 62.3 kg of PP per (metallocene 1 g × 1 hour). VI = 398 cm ³ / g; melting point 147 ° C .; M _w = 450,000 g / mol; M _w / M _n = 2.5.
Example 21
The procedure is as described in Example 1. However, 5.2 mg of rac-31 was used. 1.67 kg of polypropylene was obtained. The activity of metallocene was 321 kg of PP per (metallocene 1 g × 1 hour). VI = 980 cm ³ / g; melting point 158 ° C.
Example 22
The procedure is as described in Example 1. However, the polymerization was carried out at 30 ° C. and 3.7 mg of rac-33 was used. 0.35 kg of polypropylene was obtained. The activity of metallocene was 94 kg PP per (metallocene 1 g × 1 hour). VI = 440 cm ³ / g; melting point 153 ° C.
Example 23
A 16 dm ³ volume dried reactor was flushed with propylene and charged with 10 dm ³ liquid propylene. H. 1.1 cm ³ of the reaction product from 2 (corresponding to 7.5 mg rac-34) was dissolved in 20 cm ³ of toluene and introduced into the reactor at 30 ° C. The reactor was heated to 50 ° C. (10 ° C./min) and held at this temperature for 1 hour by cooling the polymerization system. The polymerization was stopped by adding CO ₂ gas. Excess monomer was removed in the form of a gas and the polymer was dried at 80 ° C. under reduced pressure. 2.45 kg of polypropylene was obtained. VI = 875 cm ³ / g; melting point 160 ° C.
Example 24
A dried reactor of 16 dm ³ volume was flushed with nitrogen and charged at 10 ° C. with a 10 dm ³ benzine fraction (boiling range 100-120 ° C., aromatics removed). Nitrogen was purged from the reactor gas space by introducing 2 bar of ethylene, releasing the pressure, and repeating this operation four times. 30 cm ^{3 of} methylaluminoxane in toluene (corresponding to 45 mmol of Al, molecular weight 700 g / mol according to freezing point depression method) was added. The reactor pressure was set to 5 bar by heating the reactor contents to 30 ° C. with stirring for 15 minutes and adding ethylene at a stirring speed of 250 rpm.

In parallel with this, 3.2 g of rac-12 was dissolved in 20 cm ^{3 of a} solution of methylaluminoxane in toluene, and preactivated by standing for 15 minutes. The solution was then introduced into the reactor and the polymerization system was heated to a temperature of 50 ° C. and held at this temperature for 4 hours by cooling appropriately. During this time, the overall pressure was maintained at 5 bar by appropriately feeding ethylene.

The polymerization was stopped by adding 20 ml of isopropanol, the polymer was filtered off and dried under reduced pressure. 0.7 kg of polypropylene was obtained. VI = 690 cm ³ / g.
Example 25
The procedure described in Example 24 was followed. Unlike Example 23, 1.8 mg of rac-7 was used, the polymerization system was heated to 70 ° C., and this temperature was held for 1 hour. 0.9 kg of polyethylene was obtained. VI = 730 cm ³ / g.
Example 26
In a stirrable vessel, 15 g of “F-MAO on SiO ₂ ” (111 mmol of Al) was suspended in 100 cm ³ of toluene and cooled to −20 ° C. In parallel, 155 mg (0.246 mmol) of rac-5 was dissolved in 75 cm ³ of toluene and this solution was added dropwise to the suspension over 30 minutes. The mixture was gradually warmed to room temperature with stirring, at which time the suspension turned red. The mixture was then stirred at 80 ° C. for 1 hour before being cooled to room temperature, filtered, and the resulting solid was washed three times with 100 cm ³ of toluene and once with 100 cm ³ of hexane, respectively. The filtrate was red. The filter residue containing hexane was dried under reduced pressure to yield 13.2 g of a free flowing light red supported catalyst. According to the analysis, the content of zirconocene per gram of catalyst was 3.2 mg.

Polymerization: For the polymerization, 2.08 g of catalyst was suspended in a 50 cm ³ benzine fraction (boiling range 100-120 ° C., aromatic compounds removed). The polymerization was carried out at 60 ° C. in the same manner as in Example 3. 1100 g of polypropylene powder was obtained. In the reactor, no deposit was observed on the inner wall or the stirrer. Activity = 165 kg PP / (1 g × 1 hour of metallocene); VI = 1100 cm ³ / g; Melting point = 153 ° C .; M _w = 1,485,000; M _w / M _n = 3.2; MFI (230/5) ) = 0.1 dg / min; BD = 440 g / dm ³ .
Example 27
1.31 g of the catalyst from Example 26 was suspended in a 50 cm ³ benzine fraction (boiling range 100-120 ° C., aromatics removed). The polymerization was carried out at 70 ° C. in the same manner as in Example 3. 1300 g of polypropylene powder was obtained. In the reactor, no deposit was observed on the inner wall or the stirrer. Activity = 310 kg PP / (1 g of metallocene x 1 hour). VI = 892 cm ³ / g; Melting point = 150 ° C .; M _w = 1,290,000; M _w / M _n = 3.0; BD = 410 g / dm ³ .
Example 28
Except that 0.845 g of rac-5 dissolved in 500 cm ³ of toluene was reacted with 90 g of “F-MAO on SiO ₂ ” and suspended in 500 cm ³ of toluene. The procedure described in Example 26 was repeated. 84 g of a red powder catalyst was obtained. Analysis showed that the metallocene content per gram of solid was 9 mg and the red filtrate contained 13 mg of zirconium.

Polymerization: 1.1 g of the supported catalyst was suspended in 50 ml of a benzine fraction (boiling range 100-120 ° C., aromatic compounds removed). The polymerization was carried out at 70 ° C. in the same manner as in Example 3. 2850 g of polypropylene powder was obtained. In the reactor, no deposit was observed on the inner wall or the stirrer. Activity = 288 kg of PP / (1 g of metallocene × 1 hour); VI = 638 cm ³ / g; Melting point = 150 ° C .; MFI (230/5) = 0.5 dg / min; BD = 410 g / dm ³ .
Example 29
Impurities were removed from microporous polypropylene powder (AKZO) having a particle size of less than 100 μm by extraction with toluene using a Soxhlet extractor under inert conditions, and 20% by weight of trimethylaluminum in toluene Wash with concentrated solution and dry under vacuum. In parallel with this, 51.1 mg of rac-5 was dissolved in 40 cm ³ of a toluene solution of methylaluminoxane and allowed to stand for 15 minutes for complete reaction. 16.5 g of PP powder was introduced and part of the gas and the solvent in the pores of the support were removed by reducing the pressure to fully absorb the catalyst solution. By shaking the reaction vessel vigorously, a fine and free-flowing 46 g of homogeneous red powder was obtained. 10 g of supported catalyst powder was prepolymerized with ethylene for 30 minutes under inert conditions in a rotary evaporator. Mixing of the catalyst powder was carried out by maintaining the ethylene excess pressure constant at 0.1 bar with a pressure regulating valve and continuously rotating the reaction vessel while cooling to 0 ° C. 12 g of prepolymerized catalyst was obtained.

Polymerization: 4.6 g of the supported prepolymerized catalyst was suspended in 50 cm ³ of a benzine fraction (boiling range: 100-120 ° C., aromatic compounds removed). The polymerization was carried out at 70 ° C. in the same manner as in Example 3. 250 g of polypropylene powder was obtained. In the reactor, no deposits were observed on the inner wall and the stirrer, and the average particle size was 1,000 μm. Activity = 59 kg of PP / (1 g of metallocene × 1 hour); VI = 734 cm ³ / g; Melting point = 152 ° C .; BD = 390 g / dm ³ .
Example 30
For the polymerization study, while the 50 cm ³ n-decane was suspended supported non prepolymerized catalyst 1g from Example 29. The polymerization was carried out at 70 ° C. in the same manner as in Example 3. 600 g of polypropylene powder was obtained. In the reactor, thin deposits were observed on the inner wall and the stirrer, and the average particle size was 2000 μm or more. Activity = 540 kg of PP / (1 g of metallocene × 1 hour); VI = 1400 cm ³ / g; Melting point = 157.7 ° C .; BD = 280 g / dm ³ .

Claims (4)

Formula I

(Where
M ¹ is zirconium;
R ¹ and R ² are the same and are a halogen atom;
The R ³ groups are identical and are C ₁ -C ₁₀ alkyl groups;
R ^{4 to} R ¹² are the same or different and are as defined for hydrogen or R ³ , or adjacent groups of R ^{4 to} R ¹² together with the atoms connecting them form one 6-membered aromatic Forming a family ring;
R ¹³ is

Wherein R ¹⁴ and R ¹⁵ are the same or different and are a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₁₀ aryl group; and
In the synthesis of metallocenes of M ² is silicon)

How to use the bridged ligand system. A synthesis of a metallocene of formula I according to claim 1, wherein the formula E:

To use the compound. A synthesis of a metallocene of formula I according to claim 1, wherein the formula D:

To use the compound. Formula G:

Wherein R ³ groups are the same and are a C ₁ -C ₁₀ alkyl group;
R ^{4 to} R ¹² are the same or different and are as defined for hydrogen or R ³ , or the adjacent groups of R ^{4 to} R ¹² together with the atoms connecting them form one 6-membered aromatic Forming a family ring;
R ¹³ is

Wherein R ¹⁴ and R ¹⁵ are the same or different and are a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₁₀ aryl group, and M ² is silicon).